JPH0777274B2 - Method for forming monomolecular adsorption film - Google Patents
Method for forming monomolecular adsorption filmInfo
- Publication number
- JPH0777274B2 JPH0777274B2 JP63168205A JP16820588A JPH0777274B2 JP H0777274 B2 JPH0777274 B2 JP H0777274B2 JP 63168205 A JP63168205 A JP 63168205A JP 16820588 A JP16820588 A JP 16820588A JP H0777274 B2 JPH0777274 B2 JP H0777274B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- adsorption film
- monomolecular adsorption
- forming
- adsorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、分子内にジアセチレン結合を有するシラン系
単分子吸着膜を、任意の基板上に化学吸着法を用いて形
成することを特徴としたものであり、導電膜及び絶縁膜
等として半導体産業全般に利用できるものである。TECHNICAL FIELD The present invention is characterized in that a silane-based monomolecular adsorption film having a diacetylene bond in its molecule is formed on an arbitrary substrate by a chemisorption method. It can be used for the entire semiconductor industry as a conductive film, an insulating film, and the like.
従来の技術 従来より、ポリジアセチレン化合物は、分子内に非常に
長い共役ポリジアセチレン結合を有することから非線形
光学効果あるいは導電性など、機能性に富む材料として
注目されている。そこで、このポリマーをモノマー分子
から重合させて形成する手法として、より機能性の高い
結晶を得るために、ラングミュア・ブロジェット（LB）
法や真空蒸着法などが検討されている。2. Description of the Related Art Conventionally, since polydiacetylene compounds have a very long conjugated polydiacetylene bond in the molecule, they have attracted attention as a material having a high functionality such as a nonlinear optical effect or conductivity. Therefore, as a method of polymerizing this polymer from monomer molecules, Langmuir-Blodgett (LB) was used to obtain crystals with higher functionality.
Methods and vacuum deposition methods are being studied.
発明が解決しようとする課題 一般に、ポリジアセチレン化合物が、高度な光物性を有
するためには、ポリマー内に非常に長いポリジアセチレ
ン結合を必要とする。そこでラングミュア・ブロジェッ
ト（LB）法を用いればあらかじめモノマーの分子配向性
・密度を自在に制御できるので、その結果、エネルギー
線照射などに対する反応性を容易に制御できる。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Generally, a polydiacetylene compound requires a very long polydiacetylene bond in a polymer in order to have high optical properties. Therefore, if the Langmuir-Blodgett (LB) method is used, the molecular orientation and density of the monomer can be freely controlled in advance, and as a result, the reactivity to energy beam irradiation can be easily controlled.
しかし、この手法で単分子膜を作成する場合、LBトラフ
内の水面上のジアセチレンモノマーが、外部からの表面
圧にかかわらず結晶化して欠陥をつくり、結果として重
合後ある一定の長さまでの共役長しか持てないという問
題があった。However, when a monolayer is formed by this method, the diacetylene monomer on the water surface in the LB trough crystallizes to form defects regardless of the external surface pressure, and as a result, up to a certain length after polymerization. There was a problem that it could only have a conjugate length.
一方、真空蒸着法によるポリジアセチレンの形成も、膜
厚制御性など利点もあるが、製法上、過度に加熱すると
モノマーの分解が発生したりする問題があった。On the other hand, the formation of polydiacetylene by the vacuum vapor deposition method has advantages such as film thickness controllability, but there is a problem in that the monomer is decomposed when it is excessively heated in the manufacturing method.
課題を解決するための手段 本発明は上述のような、従来の問題点に鑑みなされたも
のである。すなわち、膜の分子配向性を吸着時の温度で
制御しながら、分子内にジアセチレン結合を有するシラ
ン系単分子吸着膜を化学吸着法で任意の基板上に形成す
ることを特徴とするものである。Means for Solving the Problems The present invention has been made in view of the conventional problems as described above. That is, while controlling the molecular orientation of the film by the temperature at the time of adsorption, a silane-based monomolecular adsorption film having a diacetylene bond in the molecule is formed on any substrate by the chemisorption method. is there.
作用 本発明により、膜内に欠陥を持たず、かつ分子配向性の
優れたジアセチレン系単分子吸着膜を形成することがで
きる。Effects According to the present invention, it is possible to form a diacetylene-based monomolecular adsorption film having no defects in the film and excellent in molecular orientation.
実施例 本発明の第１の実施例を第１図に基づいて説明する。第
１図（ａ）において、表面にSiO2の形成されたSi基板１
の上に、分子内にジアセチレン結合を有するシラン界面
活性剤（たとえば、CH3（CH2）ｍ−Ｃ≡Ｃ−Ｃ≡Ｃ−
（CH2）ｎ−SiCl3（m,nは整数））を用いて、10〜20℃
の温度条件のもとで化学吸着法によって、基板１の表面
で反応させ、第１図（ｂ）に示すように単分子吸着膜２
を形成する。例えば、２×10-3〜５×10-2mol/lの濃度
で溶かした80％ｎ−ヘキサン,12％四塩化炭素,8％クロ
ロホルム溶液中に浸漬し、SiO2表面で の結合３を形成する。ここで第１図（ｃ）に示すよう
に、単分子吸着膜２のジアセチレン結合４は吸着温度が
低いため基板に対して垂直に配向して成膜されている。First Embodiment A first embodiment of the present invention will be described with reference to FIG. In FIG. 1 (a), a Si substrate 1 on the surface of which SiO 2 is formed
A silane surfactant having a diacetylene bond in the molecule (for example, CH 3 (CH 2 ) m —C≡C—C≡C—
(CH 2 ) n -SiCl 3 (m, n are integers)), 10 to 20 ° C
Under the temperature conditions of 1, the reaction is carried out on the surface of the substrate 1 by the chemisorption method, and as shown in FIG.
To form. For example, it is immersed in a solution of 80% n-hexane, 12% carbon tetrachloride, 8% chloroform dissolved at a concentration of 2 × 10 −3 to 5 × 10 −2 mol / l, and the SiO 2 surface is used. To form a bond 3 of Here, as shown in FIG. 1 (c), the diacetylene bond 4 of the monomolecular adsorption film 2 is formed so as to be oriented vertically to the substrate because the adsorption temperature is low.
次に、第１図（ｄ）に示すように、赤外線などの熱線５
を膜２に対して選択的に照射すると、第１図（ｅ）に示
すように、熱線５をうけた部分６の分子は斜めに配向を
変えてしまい、結果として第１図（ｆ）に示すように、
単分子吸着膜２の中において、分子が基板に対して垂直
に配向している部分７と、斜めに配向している部分８と
が形成される。（なお、このとき、ジアセチレン化合物
は赤外線で重合されることはない。）一般に、ジアセチ
レン化合物が、エネルギー線照射などによって重合する
場合、重合するモノマー分子間においては、互いのジア
セチレン結合は斜めに配向している方が、反応性が高
い。従って、図１（ｇ）に示すように単分子吸着膜６に
対して全面に遠紫外線などのエネルギー線９を照射する
と、（ｈ）に示すように分子が垂直に配向している部分
７は未反応である一方で、分子が斜めに配向している部
分８のみが、非常に収率よく共役ポリジアセチレン結合
10を形成する。すなわち、この工程で、（ｉ）に示すよ
うな、導電性など光物性を有する部分11と、そうでない
部分12をパターン状に有する単分子吸着膜が形成された
ことになる。Next, as shown in FIG. 1 (d), heat rays 5 such as infrared rays
When the film 2 is selectively irradiated with the film 2, as shown in FIG. 1 (e), the molecules of the portion 6 receiving the heat rays 5 change their orientations obliquely, and as a result, as shown in FIG. 1 (f). As shown
In the monomolecular adsorption film 2, a portion 7 in which the molecules are oriented perpendicularly to the substrate and a portion 8 in which the molecules are oriented obliquely are formed. (At this time, the diacetylene compound is not polymerized by infrared rays.) Generally, when the diacetylene compound is polymerized by irradiation with energy rays, etc., the diacetylene bond between the polymerized monomer molecules is Reactivity is higher when it is oriented obliquely. Therefore, when the entire surface of the monomolecular adsorption film 6 is irradiated with energy rays 9 such as deep ultraviolet rays as shown in FIG. 1 (g), the portion 7 in which the molecules are vertically aligned as shown in FIG. While unreacted, only the portion 8 in which the molecules are oriented obliquely has a very good yield of conjugated polydiacetylene bond.
Forming 10. That is, in this step, as shown in (i), a monomolecular adsorption film having a pattern 11 having a part 11 having optical properties such as conductivity and a part 12 not having the same is formed.
次に、本発明の第２の実施例を第２図に基づいて説明す
る。第２図（ａ）において、表面にSiO2の形成されたSi
基板１の上に、本発明の第１の実施例の第１図（ａ），
（ｂ）と温度条件のみを50℃程度に変えた同様の化学吸
着法で、第２図（ｂ）に示すように単分子吸着膜２を形
成する。ここで、第２図（ｃ）に示すように単分子吸着
膜２のジアセチレン結合13は、吸着温度が高いため基板
に対して斜めに配向して成膜されている。Next, a second embodiment of the present invention will be described with reference to FIG. In Fig. 2 (a), Si with SiO 2 formed on the surface
On the substrate 1, FIG. 1 (a) of the first embodiment of the present invention,
A single molecule adsorption film 2 is formed as shown in FIG. 2 (b) by a similar chemical adsorption method in which only the temperature conditions in (b) and 50 ° C. are changed. Here, as shown in FIG. 2 (c), the diacetylene bond 13 of the monomolecular adsorption film 2 is formed so as to be obliquely oriented with respect to the substrate because the adsorption temperature is high.
次に、第２図（ｄ）に示すように膜全面に対して遠紫外
線などのエネルギー線９を照射すると、第２図（ｅ）に
示すように、膜内の全ての分子はあらかじめ反応のし易
い角度に配向していたために、膜全体にわたって非常に
長いポリジアセチレン結合14を形成する。従って単分子
吸着膜２は、基板表面において の結合15を形成して横方向にきれいに成膜されているた
め、第２図（ｆ）に示すようにこの工程でピンホール、
空孔など欠陥のない非常にポリジアセチレン結合の長い
ポリジアセチレンの単分子吸着膜16が形成されたことに
なる。Next, as shown in FIG. 2 (d), when the entire surface of the film is irradiated with energy rays 9 such as deep ultraviolet rays, as shown in FIG. 2 (e), all molecules in the film are preliminarily reacted. Due to the easy orientation, very long polydiacetylene bonds 14 are formed throughout the film. Therefore, the monomolecular adsorption film 2 is formed on the substrate surface. Since a bond 15 is formed to form a fine film in the lateral direction, as shown in FIG. 2 (f), a pinhole,
This means that the polydiacetylene monomolecular adsorption film 16 having a very long polydiacetylene bond and having no defects such as voids is formed.
なお、本発明に関する実験データとして、第１の実施例
の第１図（ｈ）のエネルギー線を照射されても重合しな
い部分７のUV吸収スペクトルの経時変化を第３図に、ま
た、第１図（ｈ）の重合する部分８のUVスペクトルの経
時変化を第４図にそれぞれ示す。第３図ではポリジアセ
チレンの吸収が全く発生していないが、第４図では650n
mにλmaxもつポリジアセチレンの吸収が確認されてい
る。As experimental data relating to the present invention, the time-dependent change in the UV absorption spectrum of the portion 7 of FIG. 1 (h) of the first embodiment, which is not polymerized even when irradiated with the energy rays, is shown in FIG. FIG. 4 shows the changes over time in the UV spectrum of the polymerized portion 8 in FIG. In Figure 3, absorption of polydiacetylene did not occur at all, but in Figure 4, 650n
The absorption of polydiacetylene with λ max in m has been confirmed.
発明の効果 本発明によれば、分子オーダーでピンホールがなく、し
かも遠紫外線などのエネルギー線や熱などに対する反応
性が膜内均一に制御されたジアセチレン系単分子吸着膜
の形成が可能となる。EFFECTS OF THE INVENTION According to the present invention, it is possible to form a diacetylene-based monomolecular adsorption film that has no pinholes in the molecular order and that the reactivity to energy rays such as deep ultraviolet rays and heat is uniformly controlled in the film. Become.
第１図は本発明の第１の実施例の単分子吸着膜形成方法
の工程断面図で、（ａ），（ｂ），（ｄ），（ｆ），
（ｇ），（ｉ）は基板断面図、（ｃ），（ｅ），（ｈ）
はそれぞれ（ｂ），（ｄ），（ｇ）のA,B,C部の拡大
図、第２図は本発明の第２の実施例の単分子吸着膜形成
方法の工程断面図で、（ａ），（ｂ），（ｄ），（ｆ）
は基板断面図、（ｃ），（ｅ）はそれぞれ（ｂ），
（ｄ）のD,E部の拡大図、第３図、第４図はUVスペクト
ルの経時変化を示す図でである。 １……基板、２……単分子吸着膜、3,15……結合、4,13
……ジアセチレン結合、５……熱線、６……熱線５をう
けた部分、７……分子が垂直に配向している部分、８…
…分子が斜めに配向している部分、９……エネルギー
線、10,14……ポリジアスチレン結合、11……光物性を
有する部分、12……光物性をもたない部分、16……ポリ
ジアセチレンの単分子吸着膜。FIG. 1 is a process sectional view of a method for forming a monomolecular adsorption film according to the first embodiment of the present invention, in which (a), (b), (d), (f),
(G) and (i) are cross-sectional views of the substrate, (c), (e), and (h).
Are enlarged views of A, B, and C parts of (b), (d), and (g), respectively, and FIG. 2 is a process cross-sectional view of the method for forming a monomolecular adsorption film of the second embodiment of the present invention. a), (b), (d), (f)
Is a substrate sectional view, (c) and (e) are (b) and (e), respectively.
FIG. 3D and FIG. 4 are enlarged views of the D and E parts in (d), which show changes in the UV spectrum with time. 1 ... Substrate, 2 ... Monomolecular adsorption film, 3,15 ... Bonding, 4,13
...... Diacetylene bond, 5 ... Heat rays, 6 ... Parts that receive heat rays 5, 7 ... Parts in which molecules are oriented vertically, 8 ...
… Molecularly oriented parts, 9 …… Energy rays, 10,14 …… Polydistyrene bond, 11 …… Parts with optical properties, 12 …… Parts without optical properties, 16 …… Single molecule adsorption film of polydiacetylene.
Claims (4)
がら、分子内にジアセチレン結合を有するシラン系単分
子吸着膜を、化学吸着法で任意の基板上に形成すること
を特徴とする単分子吸着膜形成方法。1. A silane-based monomolecular adsorption film having a diacetylene bond in the molecule is formed on an arbitrary substrate by a chemical adsorption method while controlling the molecular orientation of the film by the temperature at the time of adsorption. And a method for forming a monomolecular adsorption film.
吸着法によって形成した前記シラン系単分子吸着膜に対
して、パターン状に加熱処理を行った後、膜全面にエネ
ルギー線を照射することによって前記膜内に選択的に共
役ジアセチレンポリマーを形成することを特徴とする特
許請求の範囲第１項記載の単分子吸着膜形成方法。2. A silane-based monomolecular adsorption film formed by a chemical adsorption method at a low temperature of 20.degree. The method for forming a monomolecular adsorption film according to claim 1, wherein the conjugated diacetylene polymer is selectively formed in the film by irradiating the film.
吸着法によって形成した前記シラン系単分子吸着膜に対
して、膜全面にエネルギー線を照射することによって有
効共役長の長い共役ジアセチレンポリヤーを形成するこ
とを特徴とする特許請求の範囲第１項記載の単分子吸着
膜形成方法。3. A long effective conjugation length is obtained by irradiating the entire surface of the silane-based monomolecular adsorption film formed on a given substrate by a chemical adsorption method at a high temperature of 50 ° C. or higher with an energy beam. The method for forming a monomolecular adsorption film according to claim 1, which comprises forming a conjugated diacetylene polyer.
赤外線を選択的に照射することを特徴とする特許請求の
範囲第２項記載の単分子吸着膜形成方法。4. A method for performing heat treatment in a pattern,
The method for forming a monomolecular adsorption film according to claim 2, wherein infrared rays are selectively irradiated.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63168205A JPH0777274B2 (en) | 1988-07-06 | 1988-07-06 | Method for forming monomolecular adsorption film |
| EP93202997A EP0584891B1 (en) | 1988-06-28 | 1989-06-27 | Method for the formation of built-up films of monomolecular layers using silane compounds having an acetylene bond |
| EP89306531A EP0351092B1 (en) | 1988-06-28 | 1989-06-27 | Method for the formation of monomolecular adsorption films or built-up films of monomolecular layers using silane compounds having an acetylene or diacetylene bond |
| US07/371,893 US5035782A (en) | 1988-06-28 | 1989-06-27 | Method for the formation of monomolecular adsorption films or built-up films of monomolecular layers using silane compounds having an acetylene or diacetylene bond |
| DE68915873T DE68915873T2 (en) | 1988-06-28 | 1989-06-27 | Process for the production of monomolecular adsorption films or films built up from monomolecular layers using silanes containing acetylene or diacetylene bonds. |
| DE68927865T DE68927865T2 (en) | 1988-06-28 | 1989-06-27 | Process for the production of films made up of monomolecular layers using silanes containing acetylene bonds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63168205A JPH0777274B2 (en) | 1988-07-06 | 1988-07-06 | Method for forming monomolecular adsorption film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0217672A JPH0217672A (en) | 1990-01-22 |
| JPH0777274B2 true JPH0777274B2 (en) | 1995-08-16 |
Family
ID=15863738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63168205A Expired - Fee Related JPH0777274B2 (en) | 1988-06-28 | 1988-07-06 | Method for forming monomolecular adsorption film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0777274B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5671521B2 (en) * | 2009-04-02 | 2015-02-18 | データレース リミテッドＤａｔａｌａｓｅ Ｌｔｄ． | Laser imaging |
-
1988
- 1988-07-06 JP JP63168205A patent/JPH0777274B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0217672A (en) | 1990-01-22 |
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